EP2432734A2 - Mesoporous carbon materials - Google Patents
Mesoporous carbon materialsInfo
- Publication number
- EP2432734A2 EP2432734A2 EP10778301A EP10778301A EP2432734A2 EP 2432734 A2 EP2432734 A2 EP 2432734A2 EP 10778301 A EP10778301 A EP 10778301A EP 10778301 A EP10778301 A EP 10778301A EP 2432734 A2 EP2432734 A2 EP 2432734A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon material
- mesoporous carbon
- precursor composition
- acid
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/755—Nanosheet or quantum barrier/well, i.e. layer structure having one dimension or thickness of 100 nm or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
- Y10T428/24165—Hexagonally shaped cavities
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
Definitions
- the present invention relates to the field of porous carbon materials, and more particularly, to mesoporous carbon materials and films.
- Mesoporous carbon materials are three-dimensionally connected carbon frameworks containing pores within the size range of 2-50 nm (i.e., mesopores). These materials have found an increasing number of utilities, e.g., as gas separation, water purification (i.e.,, nanofiltration), catalyst support, and electrode materials.
- mesoporous carbon materials there are several problems currently being encountered in the manufacture of mesoporous carbon materials.
- One significant problem is the difficulty (i.e., slowness) of organic precursors to react (i.e., cure) in forming a polymer which functions as a carbon framework precursor.
- the polymer formation step is either incomplete, or alternatively, requires an excessive amount of time for curing to be completed (e.g., days or weeks).
- the manufacture of mesoporous carbon materials is generally conducted according to a laborious stepwise procedure, which is both time consuming and costly.
- mesoporous carbon materials are generally prone at elevated temperatures (i.e., carbonization temperatures used in their manufacture) to structural shrinkage.
- the structural shrinkage is often accompanied by a loss of mesoporosity and an onset of microporosity.
- Mesoporous carbon materials, particularly films, are also prone to cracking.
- the invention is directed to an improved method for fabricating a mesoporous carbon material. In another aspect, the invention is directed to a mesoporous carbon material produced according to the method described above.
- the method involves subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition containing the following components: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 molar (i.e., 0.5 M) concentration of a strong acid having a pKa of less than -2, wherein the carbonization conditions involve heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material.
- the strongly acidic conditions used i.e., a strong acid present in a concentration of at least 0.5M
- a more completely crosslinked (i.e., cured) polymeric carbonization precursor is produced.
- the more completely crosslinked precursor results in a mesoporous carbon material that is significantly less prone to shrinkage or cracking, particularly at elevated temperatures.
- the strongly acidic conditions permit the resulting improved carbon material to be produced in significantly less time than methods of the art, even when applied to phenolic precursor compounds generally known to have a low reactivity (e.g., phenol, deactivated phenol derivatives, and polyphenol compounds of high molecular weight, such as the tannins).
- the highly acidic conditions also permit the method to be conveniently practiced as a one-step process, i.e., wherein all components (e.g., templating components, carbon precursors, and acid) are mixed together and subjected to curing and carbonization conditions, thereby dispensing with the multi-step processes of the art.
- all components e.g., templating components, carbon precursors, and acid
- the resulting mesoporous carbon material possesses several advantageous properties, including an improved thermal stability as evidenced by a substantial absence of structural shrinkage, and/or a substantial preservation of mesoporosity, and/or a substantial preservation of BET surface area of the mesoporous carbon material, after subjecting the mesoporous carbon material to a heat-treatment temperature of at least 1800 0 C.
- FIGs. 2A-2C High-resolution SEM image (Fig. 2A) and TEM images of C-ORNL-I along the [001] (Fig. 2B) and [110] (Fig. 2C) directions.
- FIGs. 5 A,B High-resolution SEM image (Fig. 5A) and TEM image (Fig. 5B) of C- ORNL-l-c.
- Figs. 6A-6D Low-angle (Fig. 6A) and wide-angle (Fig. 6B) XRD patterns, nitrogen sorption isotherms (Fig. 6C), and pore size distribution plots (Fig. 6D) of C-ORNL-I after heat-treatment at different temperatures.
- the nitrogen sorption isotherm of C- ORNL- 1-1800 was shifted up by 50 cm 3 STP/g.
- Figs. 7A-7F High-resolution SEM images (Figs. 7A, C, E, F) and TEM images (Figs. 7B, D) of C-ORNL-I after heat treatment at different temperatures.
- the invention is directed to a method for fabricating a mesoporous carbon material.
- mesoporous indicates a material containing "mesopores", which are pores having a diameter (i.e., pore size) of between 2 and 50 ran,
- mesopores and thus, microporous materials
- macropores and thus, rnacroporous materials
- pore diameters greater than 50 nm are generally understood to have pore diameters greater than 50 nm.
- the method first involves providing (i.e., preparing or otherwise obtaining in prepared form) a precursor composition which will be subjected to a curing step followed by a carbonization step in order to produce a mesoporous carbon material of the invention.
- the precursor composition includes at least the following components: (i) a templatmg component containing a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of less than -2.
- the combination of phenolic compound/material and the crosslinkable aldehyde are herein referred to as the "polymer precursor” or “polymer precursor components”.
- the resulting polymer i.e., after polymerization and crosslinking
- the carbonization precursor i.e., the source of carbon upon being carbonized.
- the ternplating component i.e., block copolymer
- the block copolymer functions to organize the polymer precursor materials in an ordered (i.e., patterned) arrangement before the carbonization step.
- the block copolymer is typically completely volatized into gaseous byproducts, and thereby, generally does not contribute to formation of solid carbon.
- the volatile gases serve the important role of creating the mesopores in the carbon structure during the carbonization step.
- the tempi aling component can contain one or more block copolymers.
- a "block copolymer” is a polymer containing two or more chemically distinguished polymeric blocks (i.e., sections or segments).
- the copolymer can be, for example, a diblock copolymer (e.g., A-B), triblock copolymer (e.g., A-B-C), tetrablock copolymer (e.g., A-B-C- D), or higher block copolymer, wherein A, B, C, and D represent chemically distinct polymeric segments.
- the block copolymer is preferably not completely inorganic, and more preferably, completely organic (i.e., carbon-based) in order that the block copolymer is at least partially capable of volatilizing during the carbonization step.
- the block copolymer contains al ieast two segments that possess a difference in hydrophilicity or hydrophobicily (i.e., is amphiphilic).
- Such block copolymers typically form periodic structures by virtue of selective interactions between like domains, i.e., between hydrophobic domains and between hydrophilic domains.
- the block copolymer is typically linear; however, branched (e.g., glycerol branching units) and grafted block copolymer variations are also contemplated herein.
- the block copolymer contains polar groups capable of interacting (e.g., by hydrogen or ionic bonding) with the phenolic compound or material.
- the block copolymer is preferably not a complete hydrocarbon such as styrene-butadiene.
- Some of the groups preferably located in the block copolymer which can provide a favorable interactive bond with phenol groups include, for example, hydroxy, amino, imino, and carbonyl groups.
- block copolymers include those containing segments of polyacrylate or polymethacrylate (and esters thereof), polystyrene, polyethyleneoxide, polypropyleneoxide, polyethylene, polyacrylonitrile, polylactide, and polycaprolactone.
- block copolymers include polystyrene-b-poly(methylmethacrylate) (i.e., PS-PMMA), polystyrene-b- ⁇ oly(acrylic acid) (i.e., PS-PAA), ⁇ olystyrene ⁇ b-poly(4-vinylpyridine) (i.e., PS-P4VP), ⁇ olystyrene-b- ⁇ oly(2- vinylpyridine) (i.e., PS-P2VP), polyethylene-b- ⁇ oly(4-vinylpyridine) (i.e., PE-P4VP), polystyrene-b-polyethyleneoxide (i.e., PS-PEO), polystyrene-b-poly(4-hydroxystyrene), polyethyleneoxide-b-polypropyleneoxide (i.e., PEO-PPO) 5 polyethyleneoxide-b-poly(4- vinylpyridine) (PS-PMMA
- the block copolymer is a triblock copolymer containing one or more poly-EO segments and one or more poly-PPO segments. More preferably, the triblock copolymer is a poloxamer (i.e. Pluronic ® or Lutrol ® polymer) according to the general formula
- PEO polyethylene oxide block
- PPO polypropylene block
- a, b, and c represent the number of monomer units of PEO and PPO, as indicated.
- a, b, and c are each at least 2, and more typically, at least 5, and typically up to a value of 100, 120, or 130.
- Subscripts a and c are typically of equal value in these types of polymers.
- a, b, and c can independently have a value of about, or at least, or up to 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120 s 130, 140, 150, 160, 180, 200, 220, 240, or any particular range established by any two of these exemplary values.
- a and c values are each less than b, i.e., the hydrophilic PEO block is shorter on each end than the hydrophobic PPO block.
- a, b, and c can each independently have a value of 2, 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, or 160, or any range delimited by any two of these values, provided that a and c values are each less than b.
- the a and c values can be less than b by a certain number of units, e.g., by 2, 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, 45, or 50 units, or any range therein.
- a and c values are each greater than b, i.e., the hydrophilic PEO block is longer on each end than the hydrophobic PPO block.
- a, b, and c can each independently have a value of 2, 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 1 10, 120, 130, 140, 150, or 160, or any range delimited by any two of these values, provided that a and c values are each greater than b.
- the a and c values can be greater than b by a certain number of units, e.g., by 2, 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, 45, or 50 units, or any range therein.
- the b value can be a certain fraction or percentage of a and c values (or less than or greater than this fraction or percentage), e.g., about 10%, 20%, 25%, 30, 33%, 40%, 50%, 60% ; 70%, 75%, 80%, 85%, 90%, or any range delimited by any two of these values.
- the poloxamer preferably has a minimum average molecular weight of at least 500, 800, 1000, 1200, 1500, 2000, 2500, 3000, 3500, 4000, or 4500 g/mole, and a maximum average molecular weight of 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10,000, 12,000, 15,000, or 20,000 g/mole, wherein a particular range can be established between any two of the foregoing values, and particularly, between any two the minimum and maximum values.
- the viscosity of the polymers is generally at least 200, 250, 300, 350, 400, 450, 500, 550, 600, or 650 centipoise (cps), and generally up to 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, or 7500 cps, or any particular range established between any two of the foregoing values.
- the names of the poloxamers and Pluronics contain numbers which provide information on the chemical composition.
- the generic poloxamer name contains three digits, wherein the first two digits x 100 indicates the approximate molecular weight of the PPO portion and the last digit x 10 indicates the weight percent of the PEO portion.
- poloxamer 338 possesses a PPO portion of about 3300 g/mole molecular weight, and 80 wt% PEO.
- the first digit, or two digits for a three-digit number, multiplied by 300, indicates the approximate molecular weight of the PPO portion, while the last digit x 10 indicates the weight percent of the PEO portion.
- Pluronic® F- 108 (which corresponds to poloxamer 338) indicates a solid form composed of about 3,000 g/mol of the PPO portion and 80 wt% PEO.
- block copolymer can also be a reverse poloxamer of general formula:
- the block copolymer contains a linking diamine group (e.g., ethylenediamine, i.e., EDA) or triamine group (e.g., melamine).
- a linking diamine group e.g., ethylenediamine, i.e., EDA
- triamine group e.g., melamine
- Tetronics ® e.g., PEO-PPO-ED A-PPO-PEO
- reverse Tetronics ⁇ e.g., PPO-PEO-EDA-PEO-PPO
- the phenolic compound or material of the precursor composition can be any phenolic compound or material that can react by a condensation reaction with an aldehydic compound or material (e.g., formaldehyde) under acidic conditions.
- an aldehydic compound or material e.g., formaldehyde
- any compound or material containing a hydroxy group bound to an aromatic ring is suitable for the present invention as a phenolic compound or material.
- the phenolic compound or material contains one phenol group (i.e., one hydroxy group bound to a six-membered aromatic ring).
- Some examples of such compounds include phenol, the halophenols, the aminophenols, the hydrocarbyl-substituted phenols (wherein "hydrocarbyl” includes, e.g., straight-chained, branched, or cyclic alkyl, alkenyl, or alkynyl groups typically containing from 1 to 6 carbon atoms, optionally substituted with one or more oxygen or nitrogen atoms), naphthols, nitrophenols, hydroxyanisoles, hydroxybenzoic acids, fatty acid ester- substituted or polyalkyleneoxy- substituted phenols (e.g., on the 2 or 4 positions with respect to the hydroxy group), phenols containing an azo linkage (e.g., p-hydroxyazobenzene), and phenolsulfonic acids (e.g.
- halophenols include the fluorophenols, chlorophenols, bromophenols, and iodophenols, and their further sub-classification as, for example, /?-halophenols (e.g., 4-fluorophenol, 4-chlorophenol, 4-bromophenol, and 4- iodophenol), w-halophenols (e.g., 3-fluorophenol, 3-chlorophenol, 3-bromophenol, and 3- iodophenol), o-halophenols (e.g., 2-fluoro ⁇ henol, 2-chlorophenol, 2-bromo ⁇ henol, and 2- iodophenol), dihalophenols (e.g., 3,5-dichlorophenol and 3,5-dibromophenol), and trihalophenols (e.g., 3,4,5-trichlorophenol, 3,4,5-tribromophenol, 3,4,5-trifluorophenol, 3,5,6-trichlorophen
- aminophenols include 2-, 3-, and 4-aminophenol, and 3,5- and 2,5-diaminophenol.
- nitrophenols include 2-, 3-, and 4-nitrophenol, and 2,5- and 3,5-dinitrophenol.
- hydrocarbyl-substituted phenols include the cresols, i.e., methylphenols or hydroxy toluenes (e.g., o-cresol, m-cresol, p-creso ⁇ ), the xylenols (e.g., 3,5-, 2,5-, 2,3-, and 3,4- dimethylphenol), the ethylphenols (e.g., 2-, 3-, and 4-ethylphenol, and 3,5- and 2,5- diethylphenol), n -propyl phenols (e.g., 4-r ⁇ -propylphenol), isopropylphenols (e.g., 4- isopropylphenol), butylpheiio
- hydroxyanisoles include 2-methoxyphenol, 3-methoxyphenol, A- methoxyphenol, 3-?-butyl-4-hydroxyanisole (e.g., BHA), and ferulic acid.
- hydroxybenzoic acids include 2 -hydroxybenzoic acid (salicylic acid) t 3 -hydroxybenzoic acid, 4-hydroxybenzoic acid, and their organic acid esters (e.g., methyl salicylate and ethyl- 4-hydroxybenzoate).
- the phenolic compound or material contains two phenol groups.
- Some examples of such compounds include catechol, resorcinol, hydroquinone, the hydrocarbyl-1 inked bis-phenols (e.g., bis-phenol A, methylenebisphenol, and 4,4'- dihydroxystilbenc), 4,4'-biphenol, the halo-substituted diphenols (e.g., 2-haloresorcinols, 3- haloresorcinols, and 4-haloresorcinols, wherein the halo group can be fluoro, chloro, bromo, or iodo), the amino-substituted diphenols (e.g., 2-aminoresorcinoI, 3-aminoresorcinol, and 4- aminoresorcinol), the hydrocarbyl -substituted diphenols (e.g., 2,6-dihydroxytoluene, i.e., 2- methylresorcinol; 2,3
- the phenolic compound or material contains three phenol groups.
- Some examples of such compounds include phioroglucinol (1 ,3,5- trihydroxy benzene), pyrogallol (1 ,2,3-trihydroxybenzene), 1 ,2,4-trihydroxybenzene, 5- chloro-l,2,4 ⁇ trihydroxybenzene, resveratrol (trans-3,5,4'-trihydroxystilbene), the hydrocarbyl-substituted triphenols (e.g., 2,4,6-trihydroxytoluene, i.e., methylphloroglucinol, and 3,4,5-trihydroxytoIuene), the halogen-substituted triphenols (e.g., 5-chloro- 1 ,2,4- trihydroxybenzene), the carboxy-substituted triphenols (e.g., 3,4,5-trihydroxybenzoic acid, i.e., gallic acid or quinic acid, and 2,4,6-tri
- the phenolic compound or material contains multiple (i.e., greater than three) phenol groups.
- Some examples of such compounds or materials include tannin (e.g., tannic acid), tannin derivatives (e.g., ellagotannins and gallotannins), phenol-containing polymers (e.g., poly-(4-hydroxystyrene)), phenol-formaldehyde resoles or novolak resins containing at least four phenol groups (e.g., at least 4, 5, or 6 phenol groups), quercetin, ellagic acid, and tetraphenol ethane.
- tannin e.g., tannic acid
- tannin derivatives e.g., ellagotannins and gallotannins
- phenol-containing polymers e.g., poly-(4-hydroxystyrene)
- phenol-formaldehyde resoles or novolak resins containing at least four phenol groups (e.g
- the crosslinkable aldehyde component can be any organic compound or material containing an aldehyde group.
- the crosslinkable aldehyde is formaldehyde.
- organoaldehydes, organodialdehydes, and polyaldehydes e.g., organotrialdehydes, organotelraaldehydes, and so on
- organotrialdehydes, organotelraaldehydes, and so on considered herein which can serve the same purpose.
- the or gano aldehydes can be generally represented by the following formula:
- R-CHO (3) wherein R can represent a straight-chained, branched, or cyclic, and either saturated or unsaturated tiydrocarbyl group, typically containing at least 1, 2, or 3 carbon atoms, and up to 4, 5, 6, 7, or 8 carbon atoms.
- suitable organoaldehydes include acetaldehyde, propanal (propionaldehyde), butanal (butyraldehyde), pentanal (valeraldehyde), hexanal, crotonaldehyde, acrolein, benzaldehyde, and furfural.
- organodialdehydes can be generally represented by the following formula:
- dialdehyde compounds include glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, pimelaldehyde, suberaldehyde, sebacaldehyde, cyclopentanedialdehyde, terephthaldehyde, and furfuraldehyde.
- the strong acid component contains one or more acids having a pKa of or less than about -2.
- Some examples of such acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and the superacids, such as tr ⁇ flic acid.
- a molar concentration of at least 0.5 molar (i.e., 0.5 M) with respect to the total volume of precursor composition is preferred.
- the molar concentration of the acid can preferably be about or at least 0.5 M, 0.6 M, 0.7 M, 0.8 M, 1.0 M, 1.2 M, 1.5 M, 1.8 M, 2.0 M, or any range established between any two of the foregoing values.
- any one or more of the above components may also be dissolved in a suitable solvent.
- the solvent is an organic polar protic or non-protic solvent.
- organic polar protic solvents include alcohols, e.g., methanol, ethanol, n- propanol, isopropanol, ethylene glycol, and the like.
- organic polar non- protic solvents include acetonitrile, dimethylformamide, dimethylsulfoxide, methylene chloride, organoethers (e.g., telrahydrofuran or diethylether), and the like.
- an orthoacetate e.g., triethyl orthoacetate
- a weak acid i.e., having a pKa above -2
- the weak organic acids e.g.,p-toluenesulfonic acid or hypophosphorous acid
- a phenol-formaldehyde resole or novolak resin e.g., those of 500- 5000 M. W.
- a multi-step process is employed by including one or more steps before the curing and/or carbonization steps.
- a multi-step process may be employed wherein a film of the templating component in combination with the phenolic compound or material is first produced by, for example, applying (i.e., coating) said components onto a surface, and casting the components as a solid film by removing solvent therefrom (e.g., by annealing).
- the produced film may then be reacted with the crosslinkable aldehyde component (e.g., by a vapor phase reaction with, for example, formaldehyde vapor) under strong acid conditions to produce the polymerized (and optionally, crosslinked) carbon precursor material.
- the resulting cured film can then be carbonized to produce the mesoporous carbon material.
- the highly acidic condition employed in the current invention i.e., use of a strong acid of or less than a pKa less than -2 and at a concentration of at least 0.5 M
- a one-step i.e., "one-pot" preparative method.
- all components, as described above, are combined directly before the curing and carbonization steps.
- the curing step includes any of the conditions, as known in the art, which promote polymerization, and preferably, crosslinking, of polymer precursors, and in particular, crosslinking between phenolic and aldehydic components.
- the curing conditions generally include application of an elevated temperature for a specified period of time.
- other curing conditions and methods are contemplated herein, including radiative (e.g., UV curing) or purely chemical (i.e., without use of an elevated temperature).
- the curing step involves subjecting the polymer precursors or the entire precursor composition to a temperature of at least 60, 70, 80, 90, 100, 1 10, 120, 130, or 14O 0 C for a time period of, typically, at least 0.5, 1 , 2, 5, 10, or 12 hours and up to 15, 20, 24, 36, 48, or 72 hours, wherein it is understood that higher temperatures generally require shorter time periods.
- each curing step can employ any of the exemplary time periods given above.
- the gradual increase in temperature can be practiced by employing a temperature increase rate of, or at least, or no more than l°C/min, 2°C/min, 3°C/min, 5°C/min, 7°C/min, 10°C/min s 12°C/min, 15°C/min, 20°C/min, or 30°C/min, or any suitable range between any of these values.
- the gradual temperature increase can also include one or more periods of residency at a particular temperature, and/or a change in the rate of temperature increase.
- the carbonization step includes any of the conditions, as known in the art, which cause carbonization of the precursor composition.
- a carbonization temperature of about or at least 300 0 C, 350 0 C, 400 0 C, 450°C, 500 0 C, 55O°C, 600 0 C, 650 0 C, 700 0 C, 750 0 C, 800 0 C, 850 0 C, 900 0 C, 950 0 C, 1000 0 C, 1050 0 C, 1100 0 C, 1 150 0 C, 1200 0 C, 1250 0 C, 1300 0 C, 1350 0 C 5 1400 0 C, 1450°C, 1500 0 C, 1600°C, 1700 0 C, or 1800 0 C is employed for a time period of, typically, at least 1, 2, 3, 4, 5, or 6 hours and up to
- the precursor composition, or alternatively, the carbonized material can be subjected to a temperature high enough to produce a graphilized carbon material.
- the temperature capable of causing graphitization is a temperature of or greater than about 2000 0 C, 2100 0 C, 2200 0 C, 2300 0 C, 2400 0 C, 2500 0 C, 2600 0 C, 2700 0 C, 2800 0 C, 2900 0 C, 3000 0 C, 3100 0 C, or 3200 0 C, or a range between any two of these temperatures.
- the carbonization or graphitization step is conducted in an atmosphere substantially removed of oxygen, e.g., typically under an inert atmosphere.
- atmosphere substantially removed of oxygen e.g., typically under an inert atmosphere.
- inert atmospheres include nitrogen and the noble gases (e.g., helium or argon).
- each carbonization step may employ any of the exemplary time periods given above.
- the gradual increase in temperature can be practiced by employing a temperature increase rate of, or at least, or no more than l°C/min, 2°C/min, 3°C/min, 5°C/min, 7°C/min, 10°C/min, 12°C/min, 15°C/min, 20°C/min, 30°C/min, 40°C/min, or 50°C/min, or any suitable range between any of these values.
- the gradual temperature increase can also include one or more periods of residency at a particular temperature, and/or a change in the rate of temperature increase.
- the solution is stirred for a sufficient period of time (e.g., at least or about 1, 2, 5, 10, 20, 30, 40, 50, 60, 90, or 120 minutes, or a range between any these values) until the solution turns turbid.
- a sufficient period of time e.g., at least or about 1, 2, 5, 10, 20, 30, 40, 50, 60, 90, or 120 minutes, or a range between any these values.
- stirring can be continued after the onset of turbidity, such that the total amount of stirring time before curing, carbonization, or a phase- separalion process is any of the exemplary time periods given above, or a much longer period of time, such as several hours (e.g., at least or about 4, 5, 6, 7, 8, 10, or 12 hours) or days (e.g., at least or about 1, 2, 3, 4, 5, 10, J 5, or 20 days), or a range between of the foregoing exemplary periods of time.
- phase separation conditions any separation method can be applied herein.
- the phases are separated by centrifugation.
- the centrifugation can be conducted at an angular speed of or at least, for example, 2000 rpm, 2500 rpm, 3000 rpm, 4000 rpm, 5000 rpm, 6000 rpm, 7000 rpm, 8000 rpm, 9000 rpm, 9500 rpm, 10000 rpm, 11000 rpm, 12000 rpm, or 15000 rpm, or a range between any of these values, for a period of time of, for example, 0.1, 0.2, 0.5, 1 , 2, 3, 4, 5, or 6 minutes, wherein it is understood that higher angular speeds generally require less amounts of time to effect an equivalent degree of separation.
- Superspeed centrifugation e.g., up to 20,000 or 30,000 rpm
- ultracentrifugation e.g., up to 40,000, 50,000, 60,000, or 70,000 rpm
- the gel or solid phase, once separated from the liquid phase is preferably cured and carbonized in the substantial absence of the liquid phase according to any of the conditions described above for these processes.
- the produced mesoporous carbon material is in the form of a film.
- the film can have any suitable thickness.
- the film may preferably have a thickness of, or at least, or less than 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1.0 ⁇ m, 1.2 ⁇ m, 1.5 ⁇ m, 2.0 ⁇ m, 2.5 ⁇ m, 3.0 ⁇ m, 4.0 ⁇ m, 5.0 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, or 50 ⁇ m, or a range between any of these values.
- the film may also desirably function as part of a composite material, wherein the carbon film either overlays, underlies, or is sandwiched between one or more layers of other material.
- the other material may be porous or non-porous, and can be composed of, for example, silica, alumina, graphite, a metal oxide, or organic, inorganic, or hybrid polymer.
- the produced mesoporous carbon material is in the form of particles.
- the particles can be produced by any suitable method, such as, for example, the spray atomization techniques known in the art which also include a capability of heating at carbonization temperatures.
- the precursor composition described above typically, in a carrier solvent, such as THF or DMF
- THF or DMF can be sprayed through the nozzle of an atomizer, and the particulates directed into one or more heated chambers for curing and carbonization steps.
- a portion of the precursor composition e.g., templating agent and one of the polymer precursors, such as the phenolic
- the precursor composition may first be atomized and the resulting particles annealed (i.e., dried) by suitable conditions; the resulting particles then exposed to the other polymer precursor (e.g., formaldehyde) and subjected to strong acid conditions (as described above), followed by curing and carbonization conditions.
- the precursor composition e.g., templating agent and one of the polymer precursors, such as the phenolic
- the particles are at least or about, for example, 50 nm, 100 nm, 200 nm, 500 nm, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 10 ⁇ m, 50 ⁇ m, 100 ⁇ m, 500 ⁇ m, or 1000 ⁇ m, or a range between any two of these values.
- the mesoporous carbon material can also be functional ized, as desired, by methods known in the art for functionaiizing carbon or graphite materials.
- the carbon material may be nitrogenated, fluorinated, or oxygenated by methods known in the art.
- the carbon material may be nitrogenated, fluorinated, or oxygenated, by, for example, exposure of the carbon film, either during or after the carbonization process, to, respectively, ammonia, fluorine gas, or oxygen under suitably reactive conditions.
- the carbon material is typically placed in contact with fluorine gas for a period of several minutes (e.g., 10 minutes) up to several days at a temperature within 20 0 C to 500 0 C, wherein the time and temperature, among other factors, are selected based on the degree of fluorination desired.
- a reaction time of about 5 hours at ambient temperature typically results in fluorination of about 10% of the total carbon; in comparison, fluorination conducted at about 500 0 C for two days results in about 100% fluorination of the total carbon.
- the degree of nitrogenation, fluorination, or oxygenation can be about or at least 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 100%, or a range between any two of these values.
- the produced mesoporous carbon material contains mesopores, i.e., pores having a diameter (i.e., pore size) of 2 to 50 nm.
- the carbon material possesses the mesopores in the substantial absence of micropores (pores of less than 2 nm) or macropores (pores of more than 50 nm).
- a substantially absence of micropores or macropores is meant that no more than 5%, and more preferably, no more than about 1%, 0.5%, or 0.1% of the total pore volume is due to the presence of micropores or macropores.
- the carbon material preferably possesses mesopores having a size (diameter) of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, 30, 35, 40, 45, or 50 nm, or a range between any two of these values.
- the pores of the carbon material can also possess a level of size uniformity, i.e., in pore diameters and/or pore shape.
- the pores of the carbon material may possess an average pore diameter corresponding to any of the diameters exemplified above, subject to a degree of variation of no more than, for example, ⁇ 10 nm, ⁇ 8 nm, ⁇ 6, nm, ⁇ 5 nm, ⁇ 4 nm, ⁇ 3 nm, ⁇ 2 nm, or ⁇ 1 nm.
- the wall thickness of the mesopores is typically within the range of about 5.0-7.0 nm, e.g., 5.0, 5.5, 6.0, 6.5, or 7.0 nm, or a range between any two of these values.
- the mesopores are arranged relative to each other with a certain degree of order (i.e., in a patterned or ordered arrangement).
- a certain degree of order i.e., in a patterned or ordered arrangement.
- ordered arrangements include a hexagonal or cubic arrangement.
- the longitudinal dimension of the mesopores can have a particular orientation with respect to the surface, particularly for the case of a film.
- An orientation of mesopores substantially perpendicular to the surface is particular advantageous for the case when the carbon material (typically, a film or membrane) is applied as a gas-permeable material.
- a substantial portion of pores may have a longitudinal dimension oriented obliquely to the surface within a range of angles of, e.g., 45° to -45°, 60° to -60°, 70° to - 70°, or 80° to -80°, with respect to the surface.
- the longitudinal dimension of the mesopores it is preferred for the longitudinal dimension of the mesopores to be oriented either completely aligned (i.e., parallel) with the surface (i.e., precisely 0°), or substantially aligned to the surface, e.g., 0 ⁇ 10°, 0 ⁇ 5°, 0 ⁇ 2°, or 0 ⁇ 1° with respect to the surface.
- a selected orientation of pores can be accomplished by, for example, carbonizing a block of precursor material and then slicing or etching a selected surface having a desired angle with respect to the longitudinal dimensions of the pores.
- a selected orientation of pores may also be accomplished by, for example, adjusting the angle of the carbon material and/or by compression by an overlayer during the carbonization step.
- the mesoporous carbon material typically possesses a BET surface area of about or at least 50, 100, 200, 300, 400, 450, 500, 550, 600, 650, 700, 750, or 800 m 2 /g, or a range between any two of these values.
- the mesoporous carbon material typically possesses a pore volume of about or at least 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, or 0.7 cm 3 /g, or a range between any two of these values.
- the mesoporous carbon material produced according to the method described above preferably possesses an improved physical resilience, such as an improved thermal stability and resistance to cracking.
- An improved thermal stability is preferably evidenced by a substantial absence of structural shrinkage, and/or a substantial preservation of mesoporosity, and/or a substantial preservation of the BET surface area after being heat- treated at a temperature of at least 1800 0 C.
- the improved thermal stability is evidenced after heat treating the mesoporous carbon material at a temperature of at least 1850 0 C, 1900 0 C, 1950 0 C, 2000 0 C, 2050 0 C, 2100 0 C, 215O 0 C 5 2200 0 C, 2250 0 C 5 2300 0 C, 235O 0 C, 2400 0 C, 2450°C, 2500 0 C, 2550 0 C, 2600 0 C, 265O 0 C, or 2700 0 C, or a range between any two of the foregoing values.
- a “substantial absence of structural shrinkage” and a “substantial preservation of BET surface area” as used herein generally means that either of these parameters change by no more than about 5%, and more preferably, no more than about 1%, 0.5%, or 0.1% after heat treatment as compared to the original value before heat treatment.
- a “substantial preservation of mesoporosity” as used herein generally means that the pore volume due to micropores or macropores does not increase by more than about 5%, and more preferably, no more than about 1%, 0.5%, or 0.1%, as compared to the total pore volume.
- the highly acidic condition employed in the present invention is primarily responsible for imparting the observed enhanced physical properties.
- the highly acidic condition promotes a self-assembly mechanism by a Coulombic (i.e., ionic) interaction between phenol groups and templating groups, as opposed to a hydrogen-bonding interaction which dominates the self-assembly mechanism under weaker acidic conditions.
- Coulombic i.e., ionic
- C-ORNL-I exhibits a type IV nitrogen sorption isotherm with a sharp capillary condensation step at relative pressure from 0.4 to 0.7 and a narrow pore size distribution, centered at 6.3 nm.
- the calculated BET surface area and pore volume are 607 m 2 /g and 0.58 cm 3 /g, respectively.
- C-ORNL-I displays three well-resolved XRD peaks which can be indexed into 100, 1 10, and 200 deflections of 2D hexagonal symmetry (p ⁇ mm), indicating a highly ordered mesostructure.
- the highly ordered 2D hexagonal structure of C-ORNL-I is further revealed by the high resolution SEM image (Fig.
- Example 1 The produced carbon material is referred to as C-ORNL-1-c.
- C-ORNL-1-c exhibits a type IV nitrogen sorption isotherm with a sharp capillary condensation step at relative pressure from 0.4 to 0.7 and a narrow pore size distribution, centered at 4,9 nm.
- the calculated BET surface area and pore volume are 418 m /g and 0.35 cm 3 /g, respectively.
- Figure 4 shows the low-angle XRD pattern of C-ORNL-1-c. A peak at 2 ⁇ - 0.83 is observed, which can be indexed into the 100 reflection of 2D hexagonal symmetry (p6mrn).
- SEM and TEM images Figs. 5 A and 5B, respectively
- Figs. 5 A and 5B, respectively of C-ORNL-1 -c clearly show a 2D hexagonal meso-structure and long range ordering.
- C-ORNL-I exhibits an unusually high degree of thermal stability.
- Figures 6A and 6B show both the low-angle and wide-angle XRD patterns of C-ORNL- ⁇ -x (herein x refers to the temperature) after heat-treatment at different temperatures, ranging from 1800°C to 2600 0 C.
- C-ORNL-I still exhibits a strong XRD peak at 2 ⁇ around 0.8° after being heated even up to 1800 0 C.
- the low-angle XRD peak becomes less visible with an increase of heat-treatment temperature, suggesting a gradual loss of mesostructural order.
- the peak position surprisingly does not shift to larger angle, thus indicating an absence of structural shrinkage.
- Figures 7A and 7B show high-resolution SEM and TEM images, respectively, of C- ORNL-I after heat treatment at a temperature of 1800°C (resulting in material referred to as CORNL-I -1800).
- Figures 7C and 7D show high-resolution SEM and TEM images, respectively, of C-ORNL-I after heat-treatment at a temperature of 2200 0 C (resulting in material referred to as CORNL- 1-2200).
- Figure 7E shows a high-resolution SEM image of C-ORNL-I after heat-treatment at a temperature of 2400 0 C (resulting in material referred to as CORNL-I -2400).
- Figure 7F shows a high-resolution SEM image of C-ORNL-I after heat-treatment at a temperature of 2600 0 C (resulting in material referred to as CORNL-I - 2600).
- the apparent hexagonal arrangement of mesopores is still observed for CORNL-I- 1800, suggesting an ordered mesostructure is maintained, which is in good agreement with the results of XRD and nitrogen sorption analysis.
- the mesoporous carbon materials being heated at higher temperatures i.e., 2200 - 2600 0 C
- exhibit wormy structures Figs. 7C-F).
- CORNL-I can be graphitized at 2400 0 C or 2600 0 C to form a highly graphitic mesoporous carbon while maintaining substantial mesoporosity and BET surface area.
- the high thermal stability of C-ORNL-I is believed to be at least partially due to the highly crosslinked resorcinol-formaldehyde polymer and resulting highly rigid carbon framework afforded by the highly acidic conditions used in the present invention.
- the thick carbon wall is also believed to contribute to the high thermal stability.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/468,946 US8114510B2 (en) | 2009-05-20 | 2009-05-20 | Mesoporous carbon materials |
PCT/US2010/035345 WO2010135389A2 (en) | 2009-05-20 | 2010-05-19 | Mesoporous carbon materials |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2432734A2 true EP2432734A2 (en) | 2012-03-28 |
Family
ID=43124736
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10778301A Withdrawn EP2432734A2 (en) | 2009-05-20 | 2010-05-19 | Mesoporous carbon materials |
Country Status (5)
Country | Link |
---|---|
US (2) | US8114510B2 (en) |
EP (1) | EP2432734A2 (en) |
JP (2) | JP2012527397A (en) |
CA (1) | CA2760937A1 (en) |
WO (1) | WO2010135389A2 (en) |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103028427A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Large-aperture carbon-loaded phosphide and preparation method of large-aperture carbon-loaded phosphide |
JP5988075B2 (en) * | 2012-02-03 | 2016-09-07 | 国立大学法人北海道大学 | Carbon material manufacturing method |
ES2907515T3 (en) | 2012-10-16 | 2022-04-25 | Martin Bakker | Catalysis by metal nanoparticles dispersed in a hierarchically porous carbon material |
WO2014060508A1 (en) * | 2012-10-18 | 2014-04-24 | Cic Energigune | Process for the preparation of hierarchically meso and macroporous structured materials |
CA2902401C (en) | 2013-02-27 | 2021-03-09 | Nisshinbo Holdings Inc. | Carbon material, fuel cell, electric double layer capacitor, carbon dioxide adsorbing device and method for producing carbon material |
US9249241B2 (en) | 2013-03-27 | 2016-02-02 | Ut-Battelle, Llc | Surface-functionalized mesoporous carbon materials |
CN103553018A (en) * | 2013-08-16 | 2014-02-05 | 同济大学 | Regular microporous carbon preparation method |
JP6327053B2 (en) * | 2013-09-13 | 2018-05-23 | 株式会社豊田中央研究所 | Porous carbon, production method thereof, and ammonia adsorbent |
EP3165506A4 (en) * | 2014-07-03 | 2018-03-14 | Toray Industries, Inc. | Porous carbon material and method for manufacturing porous carbon material |
US10392272B2 (en) | 2015-02-27 | 2019-08-27 | Ut-Battelle, Llc | Modulation of ion transport in a liquid by application of an electric potential on a mesoporous carbon membrane |
US10081548B2 (en) | 2015-08-24 | 2018-09-25 | Seyyed Mohammad Ali Sharif Sheikhaleslami | Production of ordered mesoporous carbon materials |
CN105668541A (en) * | 2015-12-31 | 2016-06-15 | 陕西师范大学 | Preparation method of dozens-of-gram hierarchical pore mono-dispersed 200-300nm bowl-shaped carbon material |
CN105565296B (en) * | 2016-01-25 | 2018-01-12 | 陕西师范大学 | A kind of method that single high yield prepares the order mesoporous carbon ball of single dispersing N doping that particle diameter is 100~800 nm |
US10195587B2 (en) * | 2016-03-04 | 2019-02-05 | The Board Of Trustees Of The University Of Alabama | Synthesis of hierarchically porous monoliths by a co-gelation method |
CN105618015B (en) * | 2016-03-18 | 2018-02-09 | 西北师范大学 | A kind of preparation of three-dimensional meso-hole carbon composite and its application as solid phase micro-extraction fabric coating material |
KR101983675B1 (en) * | 2016-06-13 | 2019-09-03 | 이화여자대학교 산학협력단 | Porous carbonaceous structure formed by using porous geopolymer, method of preparing the same, and use of the same |
US10702852B2 (en) | 2016-06-16 | 2020-07-07 | Ut-Battelle, Llc | Amidoxime-functionalized materials and their use in extracting metal ions from liquid solutions |
CN106744793B (en) * | 2016-12-01 | 2019-04-05 | 中国林业科学研究院林产化学工业研究所 | A kind of alkali lignin based super capacitor porous carbon material and its preparation method and application |
US20200331756A1 (en) * | 2017-10-05 | 2020-10-22 | ImMutriX Therapeutics, Inc. | Novel carbon foams and methods of making and using same |
TWI647175B (en) | 2017-10-25 | 2019-01-11 | 台灣中油股份有限公司 | Method for making multi-pore carbon materials by using bio-oils |
EP3476818A1 (en) * | 2017-10-27 | 2019-05-01 | Heraeus Battery Technology GmbH | A process for the preparation of a porous carbon material using an improved carbon source |
EP3476817A1 (en) | 2017-10-27 | 2019-05-01 | Heraeus Battery Technology GmbH | A process for the preparation of a porous carbon material using an improved amphiphilic species |
CN109675507B (en) * | 2019-01-22 | 2021-09-07 | 齐鲁工业大学 | Preparation method of micron-sized melamine resin balls |
US11154152B2 (en) | 2019-02-01 | 2021-10-26 | Jerry R. Hammar | Mailbox support system |
EP3718966A1 (en) * | 2019-04-02 | 2020-10-07 | Heraeus Battery Technology GmbH | Process for preparing a macroporous carbon material and a porous carbon material obtainable by this process |
CN112758910B (en) * | 2019-11-04 | 2023-11-24 | 中国科学院大连化学物理研究所 | Mesoporous nano carbon sphere and preparation method and application thereof |
JP7426216B2 (en) * | 2019-11-27 | 2024-02-01 | 株式会社日本触媒 | Carbon material manufacturing method and carbon material |
JP7153005B2 (en) * | 2019-11-29 | 2022-10-13 | 株式会社豊田中央研究所 | MESOPOROUS CARBON, METHOD FOR MANUFACTURING SAME, AND POLYMER FUEL CELL |
US20240002234A1 (en) * | 2021-04-14 | 2024-01-04 | Kolon Industries, Inc. | Method for preparing porous carbon structure having increased surface area and total pore volume, and porous carbon structure prepared using same |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4439349A (en) * | 1980-04-28 | 1984-03-27 | Everett Douglas H | Mesoporous carbons |
JP3628399B2 (en) * | 1995-10-18 | 2005-03-09 | カネボウ株式会社 | Activated carbon for adsorption of organic chlorine compounds |
GB0019417D0 (en) * | 2000-08-09 | 2000-09-27 | Mat & Separations Tech Int Ltd | Mesoporous carbons |
JP2005060849A (en) * | 2003-08-11 | 2005-03-10 | Toray Ind Inc | Porous carbon fiber and method for producing the same |
JP2005314223A (en) * | 2004-03-30 | 2005-11-10 | Kobe Steel Ltd | Porous carbon material and method for producing the same |
US20060057051A1 (en) * | 2004-09-10 | 2006-03-16 | Sheng Dai | Highly ordered porous carbon materials having well defined nanostructures and method of synthesis |
US8648009B2 (en) * | 2006-04-27 | 2014-02-11 | The Penn State Research Foundation | Method for the synthesis of porous carbon materials |
JP5496448B2 (en) * | 2007-09-27 | 2014-05-21 | エア・ウォーター・ベルパール株式会社 | Molecular sieve carbon, method for producing the same, and nitrogen generator |
US20080152577A1 (en) * | 2006-12-21 | 2008-06-26 | Addiego William P | Ordered mesoporous carbons and method for manufacturing same |
US9017837B2 (en) * | 2008-02-19 | 2015-04-28 | Cabot Corporation | High surface area graphitized carbon and processes for making same |
-
2009
- 2009-05-20 US US12/468,946 patent/US8114510B2/en not_active Expired - Fee Related
-
2010
- 2010-05-19 EP EP10778301A patent/EP2432734A2/en not_active Withdrawn
- 2010-05-19 WO PCT/US2010/035345 patent/WO2010135389A2/en active Application Filing
- 2010-05-19 CA CA 2760937 patent/CA2760937A1/en not_active Abandoned
- 2010-05-19 JP JP2012511979A patent/JP2012527397A/en active Pending
-
2012
- 2012-01-19 US US13/353,722 patent/US8513319B2/en active Active
-
2014
- 2014-08-01 JP JP2014157444A patent/JP2014208593A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO2010135389A3 * |
Also Published As
Publication number | Publication date |
---|---|
US20100297389A1 (en) | 2010-11-25 |
JP2012527397A (en) | 2012-11-08 |
CA2760937A1 (en) | 2010-11-25 |
JP2014208593A (en) | 2014-11-06 |
US20120121498A1 (en) | 2012-05-17 |
US8513319B2 (en) | 2013-08-20 |
WO2010135389A3 (en) | 2011-02-17 |
US8114510B2 (en) | 2012-02-14 |
WO2010135389A2 (en) | 2010-11-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8513319B2 (en) | Mesoporous carbon materials | |
US10626028B2 (en) | Carbon composition with hierarchical porosity, and methods of preparation | |
US8828533B2 (en) | Mesoporous carbon materials | |
US20140227325A1 (en) | Lignin-derived porous carbon composition, methods of preparation, and use thereof | |
US20150306570A1 (en) | Metal-carbon composites and methods for their production | |
US10017391B2 (en) | Direct polymer templating synthesis of mesoporous carbon | |
US10081548B2 (en) | Production of ordered mesoporous carbon materials | |
US10008338B2 (en) | High temperature oxygen treated carbon aerogels | |
US20150284252A1 (en) | Process for the preparation of hierarchically meso and macroporous structured materials | |
US20070167534A1 (en) | High strength air-dried aerogels | |
TW201130557A (en) | Composite silicone membranes of high separation efficiency | |
JP6309386B2 (en) | Carbon catalyst and method for producing the same | |
Nam et al. | Preparation of macroporous carbon foams using a polyurethane foam template replica method without curing step | |
Uddin Ahmad et al. | Adsorptive removal of resorcinol onto surface modified ordered mesoporous carbon: kinetics and equilibrium study | |
JP5988075B2 (en) | Carbon material manufacturing method | |
CN113603077A (en) | Preparation method of high-adsorption-force spherical mesoporous carbon | |
Šupová et al. | Relation between mechanical properties and pyrolysis temperature of phenol formaldehyde resin for gas separation membranes | |
US10392272B2 (en) | Modulation of ion transport in a liquid by application of an electric potential on a mesoporous carbon membrane | |
Yamazaki et al. | Nanostructured carbonaceous material with continuous pores obtained from reaction-induced phase separation of miscible polymer blends | |
JP4915900B2 (en) | Porous carbon membrane having controlled mesopores and method for producing the same | |
JP5062591B2 (en) | Honeycomb structure | |
JP4173061B2 (en) | Method for producing organic polymer gel | |
JP2020083661A (en) | Carbon porous body and method for producing carbon porous body | |
WO2019222009A1 (en) | Processes for making phenolic-aldehyde polymer gels and carbon materials produced therefrom | |
CN116675896B (en) | Phenolic resin sponge material with asymmetric structure and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20111216 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: WANG, XIQING Inventor name: DAI, SHENG |
|
DAX | Request for extension of the european patent (deleted) | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1168836 Country of ref document: HK |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20151201 |
|
REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1168836 Country of ref document: HK |